Vat dyestuff of the thionaphthene-indigoid series



Patented Dec. 13, 1932 UNITED STATES PATENT OFFICE WILHELM BAUER AND JOSEF HAL-LEE, OF LEVERKUSEN-WIESDORF, AND GEORG BOSCH, OI? COLOGNE-MULHEIM, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NERV YORK, N. Y A CORPORATION OF DELAWARE VAT DYESTUFF OF 'lE-IE THIONAPHTHENE-INDIGOID SERIES No Drawing. Application filed March 19, 1931, Serial No. 523,932, and in Germany March 21, 1930.

The present invention relates to new vat dyestuffs being at the same time of themdigoid and anthraquinoid type, more particularly it relates to dyestuffs of the probable general formula J- (CO.NH.A)n

CO-NH-A CO-NH-A In these formulae R and R mean substituted or-unsubstituted benzene or naphthalene nuclei, A a substituted or unsubstituted anthraquinone nucleus and n one of the numbers l or 2. The -CO-NHA group is linked to an aromatic nucleus of the indigoid radical of the dyestuffs.

It is known that by the condensation of '1 hydroxythionaphthenes with isatins vat dyestuffs of the indigoid series can be obtained. The products produced from unsubstituted isatin are of small value as vat dyestuffs, since they either decompose in the vat or, even when they can be vatted without decomposition,'possess only little affinity to the vegetable fibre and are only converted into useful vat dyestuffs by halogenation.

In accordance with the present invention vat dyestuffs of superior tinctorial properties are obtained, when the above specified indigoid compounds are substituted in the carbocyclic ring of the isatin residue by a carbonyl-aminoanthraquinone group Dyestuffs of this kind can be obtained, for example, in the following manner An isatin carboXylic acid is first condensed with hydroxy-thionaphthene or a homologue, or nuclear substitution product thereof, which may also be derived, for example, from naphthalene. For the condensation also such compounds may be used, as are converted during the reaction into hydroXy-thionaphthenes, such as for example, the corresponding carboxvlic acids, acetyl derivatives and the like. Thus are obtainable indigoid compounds, which still contain a carboxylic acid group in the carbocyclic ring system of the isatin residue and are consequently sensitive to alkali. When the carboxylic acid is now converted into the acid chloride or some other reactive carboxylic acid derivative and this ride in ten times the quantity of orthothis process the same dyestuffs are formed as in the process previously described.

In accordance with a further feature of the present invention a hydrogen atom of the carbocyclic ring system of the thionaphthene residue in indigoid vat dyestuffs is replaced by a carbonyl-aminoanthraquinone group. By condensing hydroxy-thionaphthenes containing a carboxylic acid group in the carbocyclic ring system, or reactive a-derivatives or nuclear substitution products thereof, with the components customarily used for the manufacture of indigoid dyestuffs, for example, withcyclic o-diketones or cyclic compounds containing a reactive COCH -group, or reactive (Jr-derivatives thereof, which compounds may likewise contain a carboxylic acid group attached to a carbocyclic ring system, indigoid dyestuffs are obtained, containing one or two carboxylic acid groups in the carbocyclic ring systems. By oxidizing hydroxy-thionaphthenes containing a carboxylicacid group in the carbocyclic ring system, or substitutionproducts thereof, for example, with potassium ferri-cyanide or air in the presence of copper salts, there are obtained thioindigos containing carboxylic acid groups as substituents. The carboxylic acid groups of all these indigoid dyestuffs can be caused to react in the customary manner, for example, after transformation into the corresponding acid chlorides, with aminoanthraquinones. In this manner new vat dyestuffs are likewise obtained, which are at the same time of the indigoid and anthraquinoid type. I

The new vat dyestuffs obtainable according to the processes described above, form yellowish-orange to black crystals, diificultly soluble in theusual organic solvents, soluble in strong sulfuric acid with most various colorations. They can be vatted easily, have a good aflinity to textile fibres and yield, especially on cotton, clear and full dyeings possessing good fastness properties. The dyestuffs are, moreover, likewise well suited for calico printing.

Y The following examples illustrate our invention, without, however, restricting it thereto, the parts being by weight Example 1 191 parts of finely powdered isatin-7-c'arboxylic acid and 185'parts of 5-chlorohydroxy-thionaphthene are heated to 100 C., with stirring, in 2000 parts of glacial acetic acid with the addition of 10 parts of hydrochloric acid, until the condensation is complete. The 'dyestuif, which separates in the calculated amount in the form of a red precipitate, is isolated, washed and dried.

357 parts of the finely powdered intermediate product are heated, with stirring, to 150-160 C. with 250 parts of thionyl chlo dichlorobenzene. Partial solution occurs with evolution of sulfur dioxide and hydrochloric acid and the acid chloride immediately separates. As soon as the reaction is complete, which is shown by the slackening of the evolution of gases, the reaction mass is allowed to cool. The chloride, which separates in a crystalline form, is filtered, washed and dried.

37 5 parts of this chloride are heated to 160180 (1., while stirring, with 223 parts of alpha-aminoanthraquinone in nitrobenzene. Temporary solution occurs and with evolution of hydrochloric acid the dyestuff immediately begins to separate while still hot. As soon as the evolution of gas has slackened, the reaction mixture is allowed to cool somewhat. The dyestuff is then filtered while still hot, washed and dried. It forms a red crystalline'powder, which is nearly insoluble in the usual organic solvents. The coloration of the solution in sulfuric acid is olive brown. With alkaline hydrosulfite it yields a reddish-brown vat, from which cotton, after oxidation and soaping, is dyed deep clear yellowish red shades, which are distinguished by superior fa'stness to boiling and chlorine. The new product most probably corresponds to the formula NHO E wample 2 From 191 parts of isatin-7-carboxylic acid and 200 parts of 4.5-benzo-hydroxy-thionaphthene the indigoid intermediate product is produced as described in Example 1 and is obtained as a brown powder. 373 parts of this powder are converted by heating with 250 parts of thionyl chloride in ortho-dichlorobenzene into the acid chloride, which, after isolation, forms a crystalline blackish-brown powder. 391 parts of this powder are condensed to the dyestuff by heating with 223 parts of alpha-aminoanthraquinone in nitrobenzene. The yield exceeds 80%. The dyestu'lf is a brown crystalline powder,'which is nearly insoluble in the usual organic solvents even on heating. It dissolves in sulfuric acid with a dull violet coloration. On pouring this solution into water, the dyestufi' separates in the form of brown flakes. The dyestuff yields with alkaline hydro'sulfite a reddish-brown vat, from which cotton, after oxiably corresponds to the formula tion.

00 I IH (I) Ewa'mple 3 225 parts of 5-chloro-isatin-7-carboxylic acid are heated to 120 C. for one hour, while stirring, with 184 parts of 5-chlorohydroxythionaphthene in 2000 parts of chlorobenzene after the addition 'of 20 parts of phosphorus oxychloride. The red dyestuff, which separates, is filtered after cooling, washed and dried.

391 parts of this dyestuif are converted into the acid chloride by heating with 250 parts of thionyl chloride as described in Example 1, the acid chloride is isolated and dried.

409 parts of this chloride, most finely powdered are heated to 190 0., while stirring, with 342 parts of 1-amino-5-benzoylamino anthraquinone in nitrobenzene, until the evolution of hydrochloric acid gas ceases. The.

dyestufi, which separates while stillhot, is filtered at 100 (3., washed and dried. 'It forms a red powder, which is nearly insoluble in the usual organic solvents and dissolves in sulfuric acid with a blackish-violet colora- From the dark violet vat cotton is dyed a violet black. After oxidation and soaping, a clear, powerfuland very fast orange-red is obtained. The new product most probably corresponds to the formula The hitherto unknown 5chloro-isatin-T-carboxylic acid can be obtained from isatin-7- carborzylic acid by chlorination in chlorobenzene by means of sulfuryl chloride. It forms an intense yellow crystalline powder, which decomposes at 260 C.

Ewample 4 191 parts of isatin-5-carboxylic acid are heated to 120 C. for one hour, while stirring, with 180 parts of 6-methoXy-hydroxythionaphthene in chlorobenzene after the addition of 10 parts of phosphorus oxy-chloride. The orange colored dyestuf't, which separates, is isolated and very finely powdered.

353 parts of this dyestufi" are converted by heatingwith 250 parts of thionyl chloride, with stirring, in a manner analogous to that described in Example 1, into the acid chloride, which separates while still hot as an orange colored crystalline precipitate. It is isolated, washed and dried.

371 parts of this product are heated to 190 C. with 223 parts of alpha-aminoanthraquinone in nitrobenzene, until the reaction, which proceeds with evolution of hydrochloric acid, is complete. The dyestuff, which separates while still hot, is filtered hot, washed and dried. It forms an orange colored powder, which is nearly insoluble in the usual organic solvents. The solution in sulfuric acid is yellowish-red. From the reddish-brown hydrosulfite vat vegetable and animal fibers are dyed brown shades. After 1 oxidation and soaping a fast yellowishorange is obtained. The new product most probably corresponds to the formula The hitherto unknown isatin-5-carboxylic acid can easily be obtained from para-aminobenzoic acid ester by the process described by Sandmeyer (Helvchim. acta, 1919, page 238) It forms a light yellow powder, which dissolves in cold sodium carbonate solution with a yellow coloration. On the cautious addition of caustic soda the solution becomes dark brown, but quickly turns to light yellow again. The acid sinters at 250 C. but is still unmelted at 280 C.

Example 5 191 parts of isatin-7-carboxylic acid are heated to 100 C. for 2 hours, with stirring, under a reflux condenser with 250 parts of thionyl chloride in 1000 parts of chlorobenzene. Sulfur dioxide and hydrochloric acid are evolved. Thetemperature is maintained, until the evolution of gases ceases. After cooling, the isatin-7-carboxylic acid chloride, which separates in form of yellow crystals, is filtered, washed with chloroben zene and dried.

210 parts of this chloride are heated gradually to 150 C., while stirring, with 223 parts of alpha-aminoanthraquinone and 1500 parts of ortho-dichlorobenzene, whereupon after temporary solution the isatin 7-carbonyl-alpha-aminoanthraquinone separates in a crystalline form while still hot. Heating is continued, until the evolution of hydrochloric acid gas and therewith the reaction is complete. The substance which separates is, after cooling, isolated in the customary manner, It forms a yellowish crystalline powder, which is still unmelted at 280 C. It yields abluish red vat and gives light yellow dyeings on cotton.

396parts of this productand 200 parts of 4.5-benzo-hydroxy-thionaphthene are heated to 150 0., with stirring,.in 5000 parts of ortho-dichlorobenzene, and 20 parts of phosphorous oxychloride are added. After a short time the separation of the dyestuif begins. As soon as the reaction is complete, the dyestufi is filtered while still hot, washed with chlorobenzene and dried.

It is identical with that obtainable in accordance with Example 2. I

The above examples can be modified, as desired, by using other hydroXy-thionaphthenes, isatins or aminoanthraquinones, whereby dyestuifs of the most varied shades can be obtained. In the following table a number of such dyestuffs is set forth:

ortho-dichlorobenzene into the acid chloride, which, after isolation, forms a crystalline scarlet-red powder. 390 parts of this chloride are condensed to the dyestuif by heating with 223 parts by weight of beta-aminoanthraquinone in nitrobenzene. The yield exceeds 90%. The dyestuff is a scarlet-rod crystalline powder, which is nearly insoluble in the usual organic solvents. It dissolves in sulfuric acid with a deep red coloration. From this solution the dyestufi" is obtained in orange red flakes on pouring the solution into water. The dyestuif yields with alkaline hydrosulfite a yellowish'brown vat, from which cotton, after oxidation and soaping, is dyed clear scarlet-red shades of good fastness properties, especially to chlorine and soaping. The new dyestuff most probably corresponds to the formula 124 parts of Q-amino-terephthalic acid are dissolved in 500 parts of hot water, to which have been added 182 parts of 33% aqueous Isatin components Hydroxythionaphthene components Anthraquinone components Dyeing on cotton Isatin-7-carboxylic acid Isatin-7-carboxyiic acid Isatin-Tcarboxylic acid Isatin-7-carboxyiic acid Isatin-7-carboxyiic acid Isatin-7-carboxy1ic acid Isatin-7-carboxy1ic acid Isatin-7-carboxyiic acid Isatin-T-carboxyiic acid Isatin-7-ca-rboxylic acid Isatin-7-carboxylic acid G-ethoxy-hydroxythionaphthene fi-ethoxy-hydrc;.ythionaphthene 6-methoxy-hydroxythionaphthene 4.6-dimethy1-hydroxythionaphthene ligfijlgg'l-fi-Chhfohyd roxythionaph- 4.6-dimethyl-hydroxythionaphthene 5.6.7-trichlorohydroxythionaphthene 4 7-dimcthy1- 5-chioroh3 'droxythionaphthene 5-ch1orc-hydroxythionaphthene 4 5-bromohydroitythionaphthene 4 7-dim ethyl-5-chlorohydroxythionaphthene 4.5-benzohydroxythionaphthene Bz-4-chloro-6.7-benzohydroxythionanhthene (see Br. Pat. No. 222,

120) 5.G-henm-7-ch1orohydroxythionaphthene G-methoxy-hydroxythionaphthene 3-chlorohydroxythionaphthene 4-inlethyl-G-chiorohydroxythionapht ene fi-aminoanthraquinone a-aminoanthraquinone 1-amino5-benzoyiaminoanthraquinone a-arninoanthraquinone 1-am1no-5-benzoy1aminoanthraquine a-aminoanthraquinone i-aminoi-benzoylaminoanthraquinone i-amino-5-benzoylaminoanthraquinone 1 amino 5 benzoyl aminoanthraqu none a-am noanthraqu none a-am noanthraqu none dfillllIiOfiHlhlEQlllllflHB a-aminoanthraqninone i-armno-fi-benzoylammoanthraquinone a-aminoanthraquinone fl-aminoanthraquinone B-aminoanthraquinone Yellowish-orange Yeliowish-orange Yellowish-ornnge Reddish-orange Reddish-orange Red Reddish-orange BroWnish-red Red Red

Red

Reddish-brown Yeiiowish-brown Bordeaux Orange-yellow Red Scarlet-red Example 6 From 191 parts of isatin-7-carboxylic acid and 198.5 parts of l-methyl-6-chlorohydroxythionaphthene the indigoid intermediate product is produced as described in Example 1. It is obtained in this .manner in the form of a red powder. 371.5 parts of this intermediate product are converted by heating with 250 parts of thionyl chloride in sodium hydroxide solution. The solution is stirred into a mixture of 280 parts of 33% hydrochloric acid and ice. .he free acid thereupon separates as a fine paste and is diazotized with an aqueous solution of 46 parts of sodium nitrite.

Meanwhile a sodium polysulfide solution is made up from 170parts of crystallized sodium sulfide, 23 parts of sulfur and 200 parts of water containing 306 parts of 33% aqueous sodium hydroxide solution.

The diazotization mixture is then stirred at 05 G. into the sodium polysulfide solution. When the evolution of nitrogen has ceased, heating is efiected to 2530 C. The mixture is then rendered acid to Congo red, and the disulfide-tetracarboxylic acid is filtered by suction and washed with water. It is purified by dissolving it in dilute sodium carbonate solution and reprecipitating. The still damp precipitate is mixed with 1000 parts of water and 200 parts of zinc dust, and 500 parts of 33% hydrochloric acid are added slowly, while stirring at about 90100 C. After stirring, for some 3-4 hours, the l-thiophenol-2.5-dicarboxylic acid is filtered by suction, washed with water, dissolved in 1000 parts of water and 24-5 parts of 33% aqueous sodium hydroxide solution and filtered from any remaining zinc dust. 70 parts of monochloroacetic acid, dissolved in 300 parts of water, and 90 parts of 33% sodium hydroxide solution are added to the filtrate. After heating to 70 C. for half an hour, the solution is rendered acid to Congo red by means of hydrochloric acid and boiled, whereupon the separated 2.5-dicarboxyphenyl-l-thioglycollic acid is filtered, washed and dried.

The yield amounts to 125 parts by weight.

The acid is very sparingly soluble in indifferent solvents and remains unmelted at 250 C.

3-hydroxy-thionaphthene-G-carbomylic acid anhydride or nitrobenze ne. On heating to.

250 C. it remains unmelted and sublimes.

The yield amounts to 90 parts by weight. Manufacture of the dyestufl of the probable 58 parts of 3-hydroxythionaphthene-6 carboxylic acid are dissolved in dilute sodium carbonate solution and oxidized with potassium ferricyanide solution to thioindigo-6.6'- dicarboxylic acid. From the red solution the dyestuii is precipitated by means of hydrochloric acid and the red precipitate is filtered, washed with water and dried. The yield amounts to 5% parts by weight.

48 parts of finely powdered thioindigo-6.6- dicarboxylic acid are heated slowly to 160 180 C., while stirring, with 75 parts of thionyl chloride in 10 times the quantity of ortho dichlorobenzene. Evolution of sulfur dioxide and hydrogen chloride occurs with partial solution and the separation of the diacid chloride soon follows. As soon as the reaction is complete, which is perceptible from the abatement of the evolution of gases, the reaction mass is allowed to cool and the dichloride,- which separates in a crystalline form is filtered, washed and dried. The yield amounts to Q8 parts by weight.

40 parts of this di-chloride are heated to 180200 (1, while stirring with 68 parts of 1-amino-5-benzoyl-aminoanthraquinone in 10 times the quantity of nitrobenzene. The dyestuff is produced with evolution of hydrogen chloride. W'hen the evolution of hydrogen chloride has abated, the mixture is allowed to cool and the dyestufi is filtered, washed and dried;

The dyestufi forms a brown crystalline powder. With alkaline hydrosulfite it yields a reddish-brown vat, from which cotton is dyed, after oxidation and soaping, deep, clear, fast brown shades.

Example 8 Manufacture of the dyestuif of the probable formula 58 parts of '3-hydroxythionaphthene-7-carboxylic acid and 94- parts of the dimethylamino anil of 6-methoxy-3-hydroxythionaphthene are heated to 100 C. in 580 parts of glacial acetic acid, while stirring, until the mixed thioindigo has been produced. The dyestufi, which separates as a red crystalline paste in the calculated quantity, is filtered, washed and dried.

100 parts of the finely powdered interme-' diate product are heated slowly to 160180 0., while stirring, with 100 parts of thionyl chloride in 10 times the quantity of ortho dichlorobenzene. As soon as the acid chloride has been formed, heating is discontinued and the red crystalline precipitate is filtered after cooling, washed and dried. The yield amounts to 100 parts by weight.

40 parts of the chloride are heated to 180 200 C., while stirring, with 34: parts of 1- aminol-benzoylaminoanthraquinone in 10 times the quantity of nitrobenzene. The dyestuff is produced with evolution of hydrogen E wample 9 Manufacture of the dyestuff of the probable formula 58 parts of 3-hydroxythionaphthene-6-carboxylic acid and 70 parts of 1-chloro-2.-

' naphthisatin are heated to boiling, while stirring, in 580 parts of glacial acetic acid with the addition of 3 parts of hydrochloric acid, until the condensation is complete. The

dyestuff, which separates in the calculated -quantity as a reddish-brown precipitate, is

isolated, washed and dried.

95 parts of the finely powdered intermediate product are heated to 160180 C., whilestirring, with 95 parts of thionyl chloride in 10 times the quantity of ortho-dichlorobenzene. As soon as the acid chloride has been formed, heating is discontinued, and, after cooling, the brown, lustrous needles are filtered by suction, washed and dried. The

yield amounts to 95 parts by weight.

i 7 0' parts of the chloride are heated to 180- 200 C., while stirring, with 55 parts of 1 amino-4 be-nzoylaminoanthraquinone in 10 times the quantity of nitrobenzene. The dyestulf is produced with evolution of hydrogen chloride. After completion of the reaction and cooling, the reddish-brown crystalline precipitate is filtered, washed and dried. It

dissolves in concentrated sulfuric acid with a green coloration and yields with alkaline bydrosulfite a red vat, from which cotton is dyed, after oxidation and soaping, deep, fast reddish brown shades.

Example 10 Manufacture of the dyestufl of the probable formula NHCOCH45 58 parts of 3-hydroxythionaphthene-6-carboxylic acid are dissolved in 600 parts of nitrobenzene. To this solution is added at about 130 (3., while stirring, a solution of monobromo-2.l-naphthisatin-chloride 7 prepared from Parts Monobromo-2.1-naphth1sat1n 83 Dichlorobenzene 500 Phosphorous pentachloride by heating to 160180 C. with 25 parts of thionyl chloride in orthodichlorobenzene. When the evolution of sulfur dioxide and hydrogen chloride has abated and after cooling, the acid chloride is filtered, washed and dried.

47 parts of the chloride are heated to 180- 200 0., while stirring, with 35 parts of 1- amino4-benzoylaminoanthraquinone in 10 times the quantity of nitrobenzene, until the formation of the dyestuif is complete. After cooling to 80 (1., it is filtered with suction, washed. and dried. v

The dyestuff forms a black, crystalline powder, which is nearly insoluble in the usual organic solvents and dissolves in concentrated sulfuric acid with a green coloration. With alkaline hydrosulfite I it yields a reddish-' brown vat, from which cotton is dyed black shades after oxidation. lVhen in the above example the 1-amino-bbenzoylaminoanthraquinone is replaced by the same quantity of l-amino 5 benzoylaminoanthraquinone, a dyestufi is obtained, which dyes cotton from the vat olive green shades.

Emample 11 Manufacture of the dyestuff of the probable formula 40 parts of 8-hydroxythionaphthene-(l -carboXylic acid and 40 parts of acenaphthenequinone are heated to boiling, while stirring, in 400 parts of glacial acetic acid with the addition of 2 parts of hydrochloric acid, until the condensation is complete. The dyestuff, which separates in the calculated quantity as a red precipitate, is isolated, washed and dried. 35.8 parts of the finely powdered intermediate product are heated to 160-180 0., while stirring, with 29.5 parts of thionyl chloride in 10 times the quantity of orthodichlorobenzene. As soon as the acid chloride has been formed, heating is discontinued, and, after cooling, the red crystals are filtered with suction, washed and dried. The yield amounts to 36 parts by weight. 88 parts of the chloride are heated to 180-200 C., while stirring, with 34 parts of l-aminoe-benzoylaminoanthraquinone in 10 times the The dyestuif is quantity of nitrobenzene. produced with evolution of hydrogen chloride. After completion of the reaction and cooling, the red crystalline precipitate is filtered with suction, washed and dried. It yields with alkaline hydrosulfite a green vat, from which cotton is dyed, after oxidation and soaping, deep, clear, fast, scarlet-red shades.

Ewample 12 Manufacture of the dyestulf of the probable formula 0 o II ll 58 parts of 8-hydroXy-thionaphthene-7-carboXylic acid are dissolved in dilute sodium sium ferricyanide solution to thioindigo- 7.7-dicarboxylic acid. From the red solution the dyestuff is precipitated by means of hydrochloric acid, and the red precipitate is filtered, washed and dried. amounts to 54 parts by weight. 48 parts of finely powdered thioindigo-7 .7 -dicarboxylic acid are heated slowly to 160l80 (3., while stirring, with parts ofthionyl chloride in 10 times the quantity of ortho-dichlorobenzene. Evolution of sulfur dioxide and hydrogen chloride occurs with partial solution, and separation of the di-acid chloride soon follows. As soon as the reaction is complete, which is perceptible from the abatement of the evolution of gases, and after cooling, the dichloride, which separates in a crystalline form, is filtered with suction, washed and dried. The yield amounts to 48 parts by weight. V

40 parts of this dichloride are heated to 180200 0., while stirring, with 68 parts of 1-amin0-4-benzoylamino-anthraquinone in 10 times the quantity of nitrobenzene. The dyestufi is produced with evolution of hydrogen chloride. When the evolution of hydrogen chlorde has abated, and after cooling, the dyestuff is filtered, washed and dried. The dyestuff forms a reddish crystalline powder. lVith alkaline hydrosulfite it yields a bluish-red vat, from which cotton is dyed, after oxidation and soaping, clear, fast red shades.

Example 13 Manufacture of the dyestuff of the probable formula i i o o=co=o s |0 I while stirring, with 29.5 parts by Weight of thionyl chloride in 10 times the quantity carbonate solution and oxidized with potasof ortho-dichlorobenzene. As soon as the acid The yield chloride has been formed and after cooling, the red crystals are filtered with suction, washed and dried. Instead of 29.5 parts of thionyl chloride, 27 parts of phosphorous pentachloride can be employed" in a similar manner.

38 parts of the chloride are heated to 180'- 200 0., while stirring, with 34 parts of 1- amin0-4:-benzoylaminoanthraquinone in 10 times the quantity of nitrobenzene. The dyestuff is. produced with evolution of hydrochloric acid. After the completion of the reaction and cooling, the red crystalline precipitateis filtered with suction, washed and dried. It yields with alkaline hydrosulfite a Violet vat, from which cotton is dyed, after oxidation and soaping, deep, clear, red shades.

E wample 14 Manufacture of the dyestufi' of the probable formula 58 parts of 3-hydroxythionaphthene-7-car boXylic acid and 109 parts of the dimethylamino-anil of 4-1nethyl-6-chloro-3-hydroxythionaphthene are heated to 100 C. with 580 parts of glacial acetic acid, until the mixed thioindigo is formed. The red crystalline precipitate has been filtered off, washed and dried.

100 parts of this product (well powdered) are heated, whilst stirring, to 160-180 C. with 100 parts of thionyl chloride and ten times the quantity of ortho-dichlorobenzene. After the acid chloride is produced, the red crystals are filtered off from the cooled mixture, washed and dried.

40.7 parts of this chloride are heated to 180-200 0., whilst stirring, together with 22.3 parts of alpha-aminoanthraquinone in ten times the quantity of nitrobenzene. After the reaction is complete, the dye is filtered ofl", washed and dried. It is a red crystalline powder, difficultly soluble in the usual organic solvents, soluble in concentrated sulfuric acidwith a green coloration. From its alkaline hydrosulfite vat cotton isdyed fast red shades.

Thioindigos Hydtoxythionaphthene components a coupled as alpha-derivatives Anthraquinone components Dyeing on cotton 3-hydrcxythionaphthene 6 carboxylic 3 i iiroxythionaphthene -6 -carboxylic 3-iigdroxythionaphthene-6-carb0xy1ic 3 dg roxythionaphthene -6 -carboxylic 3-liydroxythionaphthene-6-carboxylic 3diiidroxythionaphthene-7-carboxy1ic 4-2gboxyhydroxythionaphthene-7-car- 6-methoxyhydroxythionaphthene 6-methoxyhydroxythionaphthene 6-methoxyhydroxythionaphthene Bz 4-ch1oro-6. 7 benzohydroxythio' naphthene Bz 4-chloro- 6.7- benzohydroxythionaphthene 5.6-benz o-7-ch1orohydroxythionaphthene 4-methy1-6-ch1orohydroxythionaph 1-amino-5-benzoylaminoanthraquinone l-aminoi-benzoylaminoanthraquinone l-aminolemetlioxy-anthraquinone l-amino-4-benzoylaminoanthraquinone 1-aminot-benzoylaminoanthraquinone 7 l-amino-fi-benzoylaminoenthraquinone I-amino-4-benzoy]aminoanthraqnin- Reddish-orange Red Red

Reddish-brown Anthracene brown Dark brown Rubin-red boxylic acid thene one Z-thionaphtltene-S-indOlG-indigos lfdiil g t fl l l if n t Isatin components Anthraquinone components Dyeing on cotton 3-hygroxythionaphthene-6-carboxylic 5.7 dich1oroisatin a-aminoanthraquinone Reddish-brown ac] 3-hygroxythionaphthene-6-carboxylic 5L7-dich1oroisatin l-aminoi-benzoylaminoanthraquim Copper-red acid 3-hydlroxythionaphthene- 7-carboxylic aci 5.7-dichloroisatin 5.7-dichloroisatin Isatin-7-carhcxy11'c acid 7 Isatin-7-carboxyiic acid Isatin-7-carboxylic acid Isatin-7-carboxy1ic acid l-chloro-2.3-naphthisatin 1-chloro-2.3-naphthisatin 5.7-dich1oroisatin one l-amino-E-benzoylaminoanthraquinone l-ainino-5-benzoy1aminoanthraquin- Brownish-red Reddish-brown Reddish-brown Copper-red Brown Red Reddish-brown Brown Reddish-brown 2-thionophthene-2-indoledndigos gg g gg ggfiggf v Islatm gg sgg gg as Anthraquinone components Dyeing on cotton 3-hygroxythionaphthene-6-carboxylic Monobromo-2.l-naphthisatin 1amino-4-benzoyiaminoanthraquin- Black aci i one 3-hygroxythionaphthene-6-carboxy1ic Mon0bromo-2.l-naphthisatin l-amino-5-henzoylaminoanthraquin- Olive green 7 am 7 one 3-hvgroxythionaphthene-fi-carboxylic 1-ch1oro-2.3-naphthisatin 1-amino-5benzoy1aminoanthraquin- Green aci one 3-hygroxythionaphthene-6-earboxylic 1-ch1oro-2.3-naphthisatin l-amino-etbenzoylaminoanthraquiu- Biuish-black aci one x Other dyestuffs g g gggggfiggg o-dikctone-components Anthraquinone components Dyeing on cotton 3=hy%roxythionaphthene-6-carboxylic Acenaphthenequinone l-aminoi-benzoylaminoanthraquin- Red e01 V. one 3-hygroxythionaphthene-7 carboxylic Acenaphthenequinone l-aminoi-bcnzoylaminoanthraquin- Red Bfil i i one 3-hygroxythionaphthene-fi-carboxylic Ogidiized to the corresponding thio- 1-amino-5-benzoylaminoanthraquin- Brown 801 1D lgO V 0119 3-hydroxythionaphthene-7-carboxylio Oxidized to the corresponding thiol-aminoi-benzoylaminoanthraquin- Red acid indigo i 3 one We claim 1. Thenew vat dyestuiis of the probable general'formula wherein J' means the radical of an indigoid dyestufi of the group consisting of thionaphthene-indole indigos thionaphthene-acenaphthene indigos and thioindigos, A stands for an anthraquinone nucleus, whichmay be substituted by halogen atoms, alkyl-alkoxy or aroylamino groups, it means one of the numbers 1 or 2, and wherein the -CO-NHA group is linked to a carbocyclic nucleus of the radical J, said dyestufi's forming yelloworange to black crystals, diificultly soluble in the usual organic solvents, dissolving in strong sulfuric acid with various colorations, dyeing cotton from an alkaline hydrosulfite vat strong orange to black shades of good fastness properties. 7 l

2. The new vat dyestuffs of the probable general formula V a Radical I wherein R and R stand for benzene or orange to brown to red crystals difiicultly soluble in the usual organic solvents ,.soluble I in strong sulfuric acid with various colorations, dyeing cotton from an alkaline hydrosulfite vat orange to brown to red shades of good fastness properties.

' '3. The new vat dyestuffs of theprobable in the usual organic solvents, soluble in strong sulfuric acid withvarious colorations, dyeing cotton from an alkalinehydrosulfite vat orange to brown to red shades of good fastness properties.

4. The new vat dyestuffs of the probable general formula Q wherein the ws mean hydrogen or one Q meanshydrogen and the other a: a'benzoylamino group, and wherein the'-'benzene nuclei of the lIldlgOId radical may be substituted by halogen atoms, alkylor alkoxy groups, said dyestuffs forming orange to red tobrown crystals, diflicultly soluble in the usual organic solvents, soluble in strong sulfuric acid with various colorations dyeing cotton from an alkaline hydrosulfite vat orange to red to brown'shades of good fastness pr0perties.-

5. The new vat dyestuffs of the probable general formula wherein R stands for a benzene or naphthalene nucleus, which may be substituted by halogen atoms, alkaylor alkoxy groups,'and vvherein the ws mean hydrogen .or one a" means hydrogen and the other 00 the benzoylamino group, said dyestuffs forming yellowish-orange to red crystals, dyeing cotton from an alkaline hydrosulfite vat yellowish-orange to red shades of goodfastness properties.

6. The new vat dyestuffs of therprobable general formula wherein the ms mean hydrogen or one w stands for hydrogen and the other w for the benzoylamino group, and wherein the nucleus marked I may be substituted by halogen atoms, alkyl or alkoxy groups, said dyestufis forming yellowish-orange to red crystals, dyeing cotton from an alkaline hydrosulfite vat yellowish-orange to red shades of'good fastness properties.

7. The newrvat dyestuffs of the probable general formula wherein R means a benzene or naphthalene nucleus, which may be substituted by halogen atoms, alkylor alkoxy groups,the ws mean hydrogen or one :0 means hydrogen and theother a: a benzoylamino group, said dyestufls forming yellowish-red to, bluish-red shadesof good fastness properties.

to dark brown crystals, dissolving in strong sulfuric acidwith various colorations, dyeing cotton from an alkaline hydrosulfite vat strong yellowish-red to bluish-red to dark brown shades of good fastness properties.

8. The new vat dyestuffs of the probable general formula wherein the ws mean hydrogen or one x means hydrogen and the other m a benzoylamino group, and wherein the CONI-I a group is linked to the nucleus marked I in 6- or 7-position, said dyestuffs forming orange to red crystals, dyeing cotton from an alkaline hydrosulfite vat strong orange to red p shades of good fastness properties. 7

10. The new dyestulf of the probable formula o=o 1 5 HIOIO 8/ 0:6 7 v \N 0 L l i O i 1 YD '125 0 NH CO.OaH

said dyestulf dyeing cotton from an alkaline hydrosulfite vat strong yellowish-orange u 11. The new dyestufi of the probable formula f said dyestufl dyeing cotton from a.reddish brown alkaline hydrosulfite vat strong red shades of good fastness properties.

12. The new dyestufi? of the probable formula 7 7 I 0 01 NH (n) C said dyestufi dyeing cotton from a brown alkaline hydrosulfite vat dark brownshades of good fastness properties. 7

In testimony whereof, We affix our signatures. WILHELM BAUER.

JOSEF HALLE-R.

GEORG Boson. 

